US3341554A - Process for preparing carboxylic acids - Google Patents
Process for preparing carboxylic acids Download PDFInfo
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- US3341554A US3341554A US320928A US32092863A US3341554A US 3341554 A US3341554 A US 3341554A US 320928 A US320928 A US 320928A US 32092863 A US32092863 A US 32092863A US 3341554 A US3341554 A US 3341554A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
Definitions
- Difunctional compounds are of considerable current interest in such areas as plasticizers, synthetic lubricants, polyesters and polyamides. Replacement of all or a major proportion of the hydrogen atoms on the carbon atoms adjacent the carboxyl groups with alkyl groups renders these difunctional compounds even more valuable because such substitution markedly improves the thermal and hydrolytic stability of these compounds.
- this invention describes a novel and economic method for preparing 2,2,4-trimethylglutaric acid compounds, particularly 2,2,4-trimethylglutaric acid- -lactone and 2,2,4-trimethylglutaric acid.
- 2,2,4-trimethylglutaric acid can be readily and economically prepared by reacting mesityl oxide with one mole of HCN under alkaline conditions to form mesitonitrile and then reacting the latter with another mole of HCN in acid media in order to form 2,2,4-trimethyl-4-cyano-y-butyrolactone.
- the latter upon hydrolysis is converted to 2,2,4-trimethyl- -glutaric acid lactone which upon catalytic reduction in an alkaline medium yields 2,2,4-trimethylglutaric acid.
- Range Preferred Range Preferred Molar ratio of HCN to mesitonitrile Between 1 and 3. 1. pH Gtol 2to1. Temp, C t. 0 to 20. Time, hrs i. 1.
- Another possible route to the 2,2,4-trimethyl-4 cyanoy-butyrolactone is from mesitonic acid. This acid may be readily produced by the hydrolysis of mesitonitrile 0 the desired 2,2,4 trimethyl 4 cyano-y-butyrolactone.
- Range Preferred Molar ratio of HON to mesitonie acid Between 1 and 3.- 1.
- pH again plays an important role in the conversion of the 2,2,4-trimethyl-4-cyanoybutyrolactone to the glutaric acid lactone.
- the reaction must be carried out in acidic media since the use of base destroys the lactone structure.
- the reaction can be most conveniently carried out in an aqueous medium at a temperature of 25 to 100 C., preferred 80 to 100 C. and a pH of from 6 to 1, preferably at 3 to 1. Any acid may be used, carboxylic or mineral, but a mineral acid such as HCl or H 80 is most convenient.
- the final step in the process is accomplished by a catalytic hydrogen of the salt of the acid lactone.
- the catalysis can be carried out in aqueous media in the presence of an excess of an alkali metal or alkaline earth metal hydroxide, preferably sodium hydroxide at temperatures between 150 and 300 C., preferably at 225 to 275 C., a reaction time of 1 to 24 hours may be used but 1 to 4 hours is preferred.
- the catalyst may be chosen from a metal selected from the group consisting of Pt, Ru, Pd or Ni, but studies indicate that Ru is best.
- the catalytic metal is preferably dispersed upon a base or support which is resistant to hot alkalies. Carbon or charcoal is preferred as the catalyst support although kieselguhr and diatomaceous earth may also be used.
- the present invention envisions the use, as a catalyst support, of a material selected from the group consisting of carbon and diatomaceous earth, with charcoal and kieselguhr being merely species thereof.
- the catalyst can be used in a concentration of from 0.05 weight percent to 10 weight percent, preferred 2 to 6 weight percent at H pressures of 100 to 10,000 p.s.i., preferred 1000 to 2500 p.s.i.
- the quantity of catalyst used may vary from about 1 to 25 weight percent based upon the acid lactone to be hydrogenated.
- the process may be simplified by combining a number of steps.
- Mesitonitrile may be directly converted to the acid lactone. This conversion may be carried out by reacting the mesitonitrile with HCN and heating the reaction mixture. Heating the reaction mixture assists the hydrolysis of the intermediately formed cyano-lactone thus producing the acid lactone.
- the conditions for the conversion of the mesitonitrile to the acid lactone are as follows:
- mesitonic acid may be converted directly to the acid lactone (13H3 u noun I E JI CH -CCHr-C-CH CH C C-COzH H COzH (7-0 The conditions for this conversion are the same as that for the mesitonitrile conversion.
- Example 1 A one liter flask equipped with a reflux condenser, stirrer, thermometer and pH electrodes was charged with 500 cc. of 50% ethanol/water and 1.1 moles (53.9 gms.) of sodium cyanide. One mole (98 gms.) of mesityl oxide was added and the reaction rapidly adjusted with HCl to pH of 9-l0 and temperature of C. The reaction was allowed to run for 4 hours, during which the pH and temperature were constantly maintained.
- the aqueous phase was acidified (pH 1) and extracted A round bottom flask equipped with stirrer, thermometer,
- the infra-red spectra of the lactone indicated the expected carbonyl bond at 5.5;]. and the absence of a nitrile bond at 4.5 The latter occurs because nitriles attached to carbon atoms attached to either oxygen or nitrogen do not give the normal nitrile absorption.
- the aqueous solution was acidified with HCl and there was an immediate precipitation.
- the ppt. was fil tered and 40.9 gms. of crude 2,2,4-trimethylglutan'c acid was obtained.
- the aqueous phase was extracted with ether and the ether phase dried over MgSO The work up of the ether extract yielded an additional 7 gms. of crude acid.
- the acid anhydride was also prepared by reacting the acid with acetic anhydride.
- the glutaric acid anhydride melted in a sealed tube at 95 C., Lit.: 95-96 C.
- Example 2 The 2,2,4-trimethylglutaric acid was also prepared in 75% yield by heating the 2,2,4-trimethylglutan'c acid-'ylactone with sodium hydroxide in a bomb at 25 0 C. for one hour, then adding the hydrogen. This procedure eliminates one step and gives a comparable yield of pure diacid.
- Raney nickel was also used for the hydrogenation. While it worked to some extent (20%), it was not as good as the ruthenium catalyst.
- Example 3 In a manner similar to that employed in Example 1, 50 gms. (0.35 mole) of mesitonic acid, prepared by the hydrolysis of mesitonitrile, was reacted with 25 gms. (0.51 mole) of sodium cyanide and 0.5 mole of sulfuric acid in water. The reaction mixture was extracted with diethyl ether and the organic phase dried over MgSO The ether and MgSO, were removed leaving 52.3 gms. of an orange liquid.
- Example 4 A round bottom flask was charged with 36 gms. (0.29 mole) of mesitonitrile, 22 gms. of NaCN and 160 cc. of H 0. To this stirred solution, at 15 C., was added one mole of H SO in 100 cc. of H 0. The reaction mixture was heated at reflux for 5 hours. After a normal workup there was 13.3 gms. of the 2,2,4-trimethyl- -glutaric acid lactone obtained, boiling point 125 to 127 C. at 0.1 mm.
- the method for preparing 2,2,4-trimethylglutaric acid compounds which comprises reacting a member of the group consisting of mesitonitrile and mesitonic acid with hydrogen cyanide at a pH of 1 to 6 at a temperature of from 0 to 120 C. for a period of from about 1 to 24 hours thereby forming 2,2,4-trimethylglutaric acid lactone and reducing the latter with hydrogen in contact with a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and in the presence of an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
- An improved method for preparing 2,2,4-trimethylglutaric acid and its salts which comprises reacting mesityl oxide and hydrogen cyanide in the presence of an alkali metal hydroxide at a pH of about 9 to 10 at a temperature of about 50 to C.
- mesitonitrile for about 4 hours to form mesitonitrile, reacting mesitonitrile with hydrogen cyanide under acidic conditions to form 2,2,4-trimethyl-4-cyano- -butyrolactone, reacting the latter with acid to form 2,2,4-trimethyl- -glutaric acid lactone and reducing the latter with hydrogen in the presence of a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
- a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
- An improved method for preparing 2,2,4-trimethylglutaric acid and its salts which comprises reacting mesityl oxide and hydrogen cyanide in the presence of an alkali metal hydroxide at a pH of about 9 to 10 at a temperature of about 50 to 80 C.
- mesitonitrile hydrolyzing the mesitonitrile to mesitonic acid, reacting the mesitonic acid with hydrogen cyanide under acidic conditions to form 2,2,4-trimethyl-4-cyano- 'y-butyrolactone, reacting the latter with acid to form 2,2,4-trimethyl-y-glutaric acid lactone and reducing the latter with hydrogen in the presence of a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
- a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
- Cited consisting essentially of a metal selected from the group Auwers Annalen def h i L 292 139 consisting of ruthenium, platinum, palladium, and 222-3.
Description
United States Patent 3,341,554 PROCESS FUR PREPARING CARBOXYLIC ACIDS Kenneth J. Murray, East Brunswick, and Allen R. Kittieson, Westlieid, NJL, assignors to Esso Research and Engineering Qornpany, a corporation of Delaware N0 Drawing. Filed Nov. 1, 1963, Ser. No. 320,928 9 Claims. (Cl. 260-3436) This invention relates to an improved method for preparing carboxylic acids and more particularly to a method for making 2,2,4-trimethylg1utaric acid compounds.
Difunctional compounds, particularly dicarboxylic acids, are of considerable current interest in such areas as plasticizers, synthetic lubricants, polyesters and polyamides. Replacement of all or a major proportion of the hydrogen atoms on the carbon atoms adjacent the carboxyl groups with alkyl groups renders these difunctional compounds even more valuable because such substitution markedly improves the thermal and hydrolytic stability of these compounds.
As indicated in US. Patent 2,820,821 issued January 21, 1958, a practicable method for the production of glutaric acid, including lower alkyl substituted and halogen substituted glutaric acids containing a total of up to seven carbon atoms or the anhydrides thereof has long been sought for. An extensive review is given in column 1, line 46 to column 2, line 47 of said patent of methods previously proposed for these preparations and the patent then discloses the preparation of these compounds by the oxidation of glutaraldehydes by means of molecular oxygen. Unfortunately, however, none of these procedures has been found suitable for commercial operation for various reasons, such as costly reactants, low yields, low quality of the product and costly equipment made necessary by the corrosive reactants.
It is the object of this invention to provide a novel method for preparing certain substituted glutaric acids.
More specifically, this invention describes a novel and economic method for preparing 2,2,4-trimethylglutaric acid compounds, particularly 2,2,4-trimethylglutaric acid- -lactone and 2,2,4-trimethylglutaric acid.
It has now been found that 2,2,4-trimethylglutaric acid can be readily and economically prepared by reacting mesityl oxide with one mole of HCN under alkaline conditions to form mesitonitrile and then reacting the latter with another mole of HCN in acid media in order to form 2,2,4-trimethyl-4-cyano-y-butyrolactone. The latter upon hydrolysis is converted to 2,2,4-trimethyl- -glutaric acid lactone which upon catalytic reduction in an alkaline medium yields 2,2,4-trimethylglutaric acid. The acid thus obtained had a melting point of l0=l102 C. (uncorrected) and a neutralization equivalent (N.E.) of 89.6.
The following reactions may be utilized in the preparation of 2,2,4-trimethylglutaric acid in accordance with the present invention.
E u H I E 1 v CH3C=CHCCH; HCN CH3COH2C=O 4 hrs/80C. I
ON Mesityl Oxide Mesitonitrile I H H+ CH3]C-CH2C-OH3 HCN CH CH (IJN CH CH2 ON [GHQ-C /OCa] Hi0 C aC 0-0113 r I EN 0 2, 2, 4-Trimethyl-4-' cyauo-y-but yrolactone 2, 2, 4-Trimethylglutaric Acid Mesityl oxide, which is readily prepared by known proc esses, is first reacted with hydrogen cyanide under alkaline conditions. The base catalyzed addition of hydrogen cyanide to mesityl oxide is extremely sensitive to reaction conditions. The products and their yields depend upon the temperature, pH, time, solvent and ratio of reactants. The conditions for the conversion of mesityl oxide to mesitonitrile are as follows:
Range Preferred Range Preferred Molar ratio of HCN to mesitonitrile. Between 1 and 3. 1. pH Gtol 2to1. Temp, C t. 0 to 20. Time, hrs i. 1.
Another possible route to the 2,2,4-trimethyl-4 cyanoy-butyrolactone is from mesitonic acid. This acid may be readily produced by the hydrolysis of mesitonitrile 0 the desired 2,2,4 trimethyl 4 cyano-y-butyrolactone.
Range Preferred Molar ratio of HON to mesitonie acid. Between 1 and 3.- 1.
6 to 1. 3 to 1. 10 to 100. to 20.
D Temp., C.-. Time, hrs-.."
As in the earlier steps, pH again plays an important role in the conversion of the 2,2,4-trimethyl-4-cyanoybutyrolactone to the glutaric acid lactone. The reaction must be carried out in acidic media since the use of base destroys the lactone structure. The reaction can be most conveniently carried out in an aqueous medium at a temperature of 25 to 100 C., preferred 80 to 100 C. and a pH of from 6 to 1, preferably at 3 to 1. Any acid may be used, carboxylic or mineral, but a mineral acid such as HCl or H 80 is most convenient.
The final step in the process is accomplished by a catalytic hydrogen of the salt of the acid lactone. The catalysis can be carried out in aqueous media in the presence of an excess of an alkali metal or alkaline earth metal hydroxide, preferably sodium hydroxide at temperatures between 150 and 300 C., preferably at 225 to 275 C., a reaction time of 1 to 24 hours may be used but 1 to 4 hours is preferred. The catalyst may be chosen from a metal selected from the group consisting of Pt, Ru, Pd or Ni, but studies indicate that Ru is best. The catalytic metal is preferably dispersed upon a base or support which is resistant to hot alkalies. Carbon or charcoal is preferred as the catalyst support although kieselguhr and diatomaceous earth may also be used. Thus, it is clear that the present invention envisions the use, as a catalyst support, of a material selected from the group consisting of carbon and diatomaceous earth, with charcoal and kieselguhr being merely species thereof. The catalyst can be used in a concentration of from 0.05 weight percent to 10 weight percent, preferred 2 to 6 weight percent at H pressures of 100 to 10,000 p.s.i., preferred 1000 to 2500 p.s.i. The quantity of catalyst used may vary from about 1 to 25 weight percent based upon the acid lactone to be hydrogenated.
The process may be simplified by combining a number of steps. Mesitonitrile may be directly converted to the acid lactone. This conversion may be carried out by reacting the mesitonitrile with HCN and heating the reaction mixture. Heating the reaction mixture assists the hydrolysis of the intermediately formed cyano-lactone thus producing the acid lactone The conditions for the conversion of the mesitonitrile to the acid lactone are as follows:
Range Preferred Molar ratio of HON to mesitonitrib...
Between 1 and 3.. 1. 6 to 1 3 Time, hrs I 1 Similarly mesitonic acid may be converted directly to the acid lactone (13H3 u noun I E JI CH -CCHr-C-CH CH C C-COzH H COzH (7-0 The conditions for this conversion are the same as that for the mesitonitrile conversion.
The following examples are illustrative of the present invention.
7 Example 1 A one liter flask equipped with a reflux condenser, stirrer, thermometer and pH electrodes was charged with 500 cc. of 50% ethanol/water and 1.1 moles (53.9 gms.) of sodium cyanide. One mole (98 gms.) of mesityl oxide was added and the reaction rapidly adjusted with HCl to pH of 9-l0 and temperature of C. The reaction was allowed to run for 4 hours, during which the pH and temperature were constantly maintained.
for V.P.C. analysis to destripping was then sent out unreacted mesityl oxide.
termine the concentration of The aqueous phase was acidified (pH 1) and extracted A round bottom flask equipped with stirrer, thermometer,
condenser and addition funnel was charged with 25 gms. of mesitonitrile (0.2 mole) and 9.8 gms. of sodium cyanide (0.2 mole) in 50 cc. of Water. The reaction temperature was lowered to 15 C. by ice cooling and 20 gms. of conc. sulfuric acid in 47 cc. of water was then added dropwise to the mixture over a period of 35 minutes. The 15 C. temperature was maintained throughout the addition.
After 40 minutes of stirring at room temperature, the reaction mixture was extracted with ether and the organic phase separated and dried over MgSO The MgSO, was filtered and the ether stripped leaving 28.35 gms. of a clear,
carbonyl and also an organic nitrile. The liquid was subjected to a vacuum distillation but no separation could be obtained. All the liquid boiled mm. A V.P.C. analysis of the liquid indicated that it was 42.9% mesitonitrile, 55.1% 2,2,4-trimethyl-4-cyano-'ybutyrolactone and 2% of a higher boiler. Separation is achieved by a careful distillation at pressures of about 100 to 200 mm. of Hg.
The lactone (B.P. 112 C. at 6.9 mm; It =l.4392; MP. 26-27 C.) was analyzed for C H NO .-Expected: 0:62.72, H=7.24, N=9.15. Found: C=62.59, H=7.34, N=8.81. The infra-red spectra of the lactone indicated the expected carbonyl bond at 5.5;]. and the absence of a nitrile bond at 4.5 The latter occurs because nitriles attached to carbon atoms attached to either oxygen or nitrogen do not give the normal nitrile absorption.
The lactone formation appears trolled since changes in reaction variables have little or no effect on the ratio of product to starting material (k e.g. is slightly greater than 1).
The cyano-lactone (25 gms., with 100 cc. of 33% initially heterogeneous reaction became homogeneous during the reaction. The solution was cooled and extracted 0.163 mole) was mixed After the reaction was completed the alcohol was stripped. The alcohol oxide were unreacted and colorless liquid. An LR. indicated 1 that the liquid containeda lactone carbonyl, a normal 1 at 68-70 C. at 0.4 I
to be equilibrium 00H".
HCl and refluxed for 4 hours. The.
three times with ether. The ether extracts were combined and dried over MgSO Removal of the ether and drying agent produced 26.6 gms. of a solid, M.P.=98 C., 95 mole percent yield. The infra-red spectra of the solid indicated that it was probably the acid lactone (2,2,4-trimethyl-'y-glutaric acid lactone). Analysis for C H O Expected: C=55.80, H=7.02. Found: :55.63, H=7.02; N.E., expected: 172. Found: 173.9. This glutaric acid lactone, not previously known, can be converted to 2,2,4-trimethylglutaric acid or it may be esterified to form solvents, plasticizers or synthetic lubricants.
Forty-four grams of pure 2,2,4-trimethyl-y-glutaric acid lactone (0.256 mole) was refluxed overnight with 84 gms. of 50% NaOH (1.05 moles) in 100 cc. of water. The solution was cooled and 5.5 gms. of ruthenium on carbon was added. The solution was then made up to 160 cc. with water and placed in a 300 ml. microbomb. The bomb was sealed, placed in a rocker, pressured up to 1900 p.s.i.g. with H and then heated to 250 C. In 24 hours there was a total uptake of 625 p.s.i.g. (expected 660) The bomb was cooled, vented and the catalyst filtered oil". The aqueous solution was acidified with HCl and there was an immediate precipitation. The ppt. was fil tered and 40.9 gms. of crude 2,2,4-trimethylglutan'c acid was obtained. The aqueous phase was extracted with ether and the ether phase dried over MgSO The work up of the ether extract yielded an additional 7 gms. of crude acid.
The crude acids were combined and recrystallized from dichloromethane. There was 36.0 gins. of pure, dry oc,cc,ot'- trimethylglutaric acid obtained (81% yield), M.P. 101- 102 C uncorrected, Lit.: 98.5-99.5 C.; N.E., Lit.: 87.0. Found: 89.6.
Analysis C H O .Lit.: 0:55.16, H=8.10. Found: 0:54.78, H=7.93.
The acid anhydride was also prepared by reacting the acid with acetic anhydride. The glutaric acid anhydride melted in a sealed tube at 95 C., Lit.: 95-96 C.
Analysis C H O .Lit.: C=61.52, H=7.75. Found: C=61.57, H=7.78.
Example 2 The 2,2,4-trimethylglutaric acid was also prepared in 75% yield by heating the 2,2,4-trimethylglutan'c acid-'ylactone with sodium hydroxide in a bomb at 25 0 C. for one hour, then adding the hydrogen. This procedure eliminates one step and gives a comparable yield of pure diacid.
Raney nickel was also used for the hydrogenation. While it worked to some extent (20%), it was not as good as the ruthenium catalyst.
Example 3 In a manner similar to that employed in Example 1, 50 gms. (0.35 mole) of mesitonic acid, prepared by the hydrolysis of mesitonitrile, was reacted with 25 gms. (0.51 mole) of sodium cyanide and 0.5 mole of sulfuric acid in water. The reaction mixture was extracted with diethyl ether and the organic phase dried over MgSO The ether and MgSO, were removed leaving 52.3 gms. of an orange liquid.
The liquid was transferred to a distillation flask and vacuum distilled. There was 29.5 gms. of the cyano lactone obtained, B.P. 109-110.5 C. at 5.2 mm. and 16.1 gms. of unreacted mesitonic acid recovered. Yield of 2,2,4-trimethyl-4-cyano-'y-butyrolactone was 0.192 mole (68% conversion with 81% selectivity).
Example 4 A round bottom flask was charged with 36 gms. (0.29 mole) of mesitonitrile, 22 gms. of NaCN and 160 cc. of H 0. To this stirred solution, at 15 C., was added one mole of H SO in 100 cc. of H 0. The reaction mixture was heated at reflux for 5 hours. After a normal workup there was 13.3 gms. of the 2,2,4-trimethyl- -glutaric acid lactone obtained, boiling point 125 to 127 C. at 0.1 mm.
The present invention is not limited to the foregoing specific embodiments since numerous variations can be made without departing from the spirit and scope ofthis invention as defined in the following claims.
What is claimed is:
1. The method for preparing 2,2,4-trimethylglutaric acid compounds which comprises reacting a member of the group consisting of mesitonitrile and mesitonic acid with hydrogen cyanide at a pH of 1 to 6 at a temperature of from 0 to 120 C. for a period of from about 1 to 24 hours thereby forming 2,2,4-trimethylglutaric acid lactone and reducing the latter with hydrogen in contact with a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and in the presence of an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
2. The method as defined in claim 1 in which the metal hydrogenation catalyst consists essentially of ruthenium upon carbon.
3. A method according to claim 1 wherein said catalyst is supported on a material selected from the group consisting of carbon and diatomaceous earth.
4. An improved method for preparing 2,2,4-trimethylglutaric acid and its salts which comprises reacting mesityl oxide and hydrogen cyanide in the presence of an alkali metal hydroxide at a pH of about 9 to 10 at a temperature of about 50 to C. for about 4 hours to form mesitonitrile, reacting mesitonitrile with hydrogen cyanide under acidic conditions to form 2,2,4-trimethyl-4-cyano- -butyrolactone, reacting the latter with acid to form 2,2,4-trimethyl- -glutaric acid lactone and reducing the latter with hydrogen in the presence of a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
5. The method as defined in claim 4 in which the metal hydrogenation catalyst consists essentially of ruthenium upon carbon.
6. An improved method for preparing 2,2,4-trimethylglutaric acid and its salts which comprises reacting mesityl oxide and hydrogen cyanide in the presence of an alkali metal hydroxide at a pH of about 9 to 10 at a temperature of about 50 to 80 C. for about 4 hours to form mesitonitrile, hydrolyzing the mesitonitrile to mesitonic acid, reacting the mesitonic acid with hydrogen cyanide under acidic conditions to form 2,2,4-trimethyl-4-cyano- 'y-butyrolactone, reacting the latter with acid to form 2,2,4-trimethyl-y-glutaric acid lactone and reducing the latter with hydrogen in the presence of a metal hydrogenation catalyst consisting essentially of a metal selected from the group consisting of ruthenium, platinum, palladium, and nickel and an excess of an alkali metal hydroxide at elevated temperatures and pressures to form the alkali metal salt of 2,2,4-trimethylglutaric acid.
7. The method as defined in claim 6 in which the metal hydrogenation catalyst consists essentially of ruthenium upon carbon.
8. The process which comprises reacting mesitonic acid in an aqueous medium with HCN in a molar ratio of from about 1:1 to about 1:3 at a pH of from 1 to 6 at a temperature of from about 0 to 20 C. for from about one hour, maintaining the aqueous medium at a temperature of from about 25 to C. for a period suflicient to convert the reaction product to 2,2,4-tritnethylglutaric acid-y-lactone and reducing the latter with hydrogen in the presence of a metal hydrogenation catalyst elevated temperatures and pressures to form the alkali 5 8 References Cited consisting essentially of a metal selected from the group Auwers Annalen def h i L 292 139 consisting of ruthenium, platinum, palladium, and 222-3.
nickel and an excess of an alkali metal hydroxide at Auwers et al.: Berichte, v0 23 P- Iwanami et al.: Kogyo Kagaku Zasshi, vol. 65 (1962),
metal salt of 2,2,4-trimethylglutaric acid.
9. The process as defined in claim 8 in which the metal WALTER A MOD ANCE Primary Examiner hydrogenation catalyst consists essentially of ruthenium NICHOLAS S. RIZZO, Examiner.
upon carbon and the reduction is eifected at between 150 and 300 C. 10 I. A. PATTEN, Assistant Examiner.
Claims (1)
1. THE METHOD FOR PREPARING 2,2,4-TRIMETHYLGLUTARIC ACID COMPOUNDS WHICH COMPRISES REACTING A MEMBER OF THE GROUP CONSISTING OF MESITONITRILE AND MESITONIC ACID WITH HYDROGEN CYANIDE AT A PH OF 1 TO 6 AT A TEMPERATURE OF FROM 0 TO 120*C. FOR A PERIOD OF FROM ABOUT 1 TO 24 HOURS THEREBY FORMING 2,2,4-TRIMETHYLGLUTARIC ACID LACTONE AND REDUCING THE LATTER WITH HYDROGEN IN CONTACT WITH A METAL HYDROGENATION CATALYST CONSISTING ESSENTIALLY OF A METAL SELECTED FROM THE GROUP CONSISTING OF. . . RUTHENIUM, PLATINUM, PALLADIUM, AND NICKEL AND IN THE PRESENCE OF AN EXCESS OF AN ALKALI METAL HYDROXIDE AT ELEVATED TEMPERATURES AND PRESSURES TO FORM THE ALKKALI METAL SALT OF 2,2,4-TRIMETHYLGLUTARIC ACID.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928275A (en) * | 1973-07-24 | 1975-12-23 | Kao Corp | Vinyl chloride resin composition containing a lubricant |
US3929712A (en) * | 1973-07-24 | 1975-12-30 | Kao Corp | Vinyl chloride type resin composition containing a lubricant |
US4130493A (en) * | 1976-07-20 | 1978-12-19 | Inoue-Japax Research Incorporated | Machining fluid |
US4788318A (en) * | 1986-11-26 | 1988-11-29 | Huls Aktiengesellschaft | Process for the production of 4,4,8,8,10-pentamethyl-10-cyano-bicyclo[4.4.0]-dec-1,6-en-2-one |
EP3137901B1 (en) * | 2014-04-29 | 2019-09-18 | SYNLAB Belgium | Method for determining urinary organic acids |
-
1963
- 1963-11-01 US US320928A patent/US3341554A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928275A (en) * | 1973-07-24 | 1975-12-23 | Kao Corp | Vinyl chloride resin composition containing a lubricant |
US3929712A (en) * | 1973-07-24 | 1975-12-30 | Kao Corp | Vinyl chloride type resin composition containing a lubricant |
US4130493A (en) * | 1976-07-20 | 1978-12-19 | Inoue-Japax Research Incorporated | Machining fluid |
US4788318A (en) * | 1986-11-26 | 1988-11-29 | Huls Aktiengesellschaft | Process for the production of 4,4,8,8,10-pentamethyl-10-cyano-bicyclo[4.4.0]-dec-1,6-en-2-one |
EP3137901B1 (en) * | 2014-04-29 | 2019-09-18 | SYNLAB Belgium | Method for determining urinary organic acids |
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